General access to ortho- and meta-alkylanilines for the synthesis of polyanilines and poly(anilines-co-substituted anilines)

Article abstract of DOI:10.1016/S0040-4020(99)00934-5

Ortho (or meta)-alkylanilines are obtained in good yields by the cross- coupling reaction of ortho(meta)-haloanilines with vinyltins in the presence of palladium catalysts.

Full text of DOI:10.1016/S0040-4020(99)00934-5

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 225–231
General Access to ortho- and meta-Alkylanilines for the Synthesis
of Polyanilines and Poly(Anilines-co-Substituted Anilines)
a
b
b
a,
*
´
ˆ
Aurelie Falcou, Didier Marsacq, Patrick Hourquebie and Alain Duchene
a
´
´
Laboratoire de Physicochimie des Interfaces et des Milieux Reactionnels, Faculte des Sciences de Tours,
Parc de Grandmont, 37200 Tours, France
b
´
´
CEA/Le Ripault, Departement Materiaux, BP 16, 37260 Monts, France
Received 8 June 1999; accepted 14 October 1999
Abstract—Ortho (or meta)-alkylanilines are obtained in good yields by the cross-coupling reaction of ortho(meta)-haloanilines with
vinyltins in the presence of palladium catalysts. ᭧ 1999 Elsevier Science Ltd. All rights reserved.
Over the last ten years, new polymers containing such
groups as a thiophene or an aniline unit1 have retained the
attention of a number of organic chemists; the numerous
potential industrial applications of these polymers, such as
sensors,2 EMI (electromagnetic interference) shielding
agents,3 corrosion inhibitors,4 and micro-electronic
devices,5 explain the great interest in the synthesis of the
monomers which are precursors of these polymers, among
which polyanilines are important conducting polymers6
because of the unique combination of electrical properties
in the doped state and environmental stability.7 Like most
conductive polymers, the commercial applications of the
conductive form of polyaniline are limited due to its poor
solubility in common organic solvents and poor process-
ability in the melted state. A common technique to increase
solubility and lower the melting point of the stiff chain is the
attachment of a flexible side-chain to the polymer back-
bone.8 In the field of conductive polymers, this concept
has been successfully applied to polythiophenes. Indeed
solubility and processability can be significantly enhanced
by introducing a flexible alkyl side chain to the thiophene
monomer.9 However, neither the conductivity of the doped
state nor the thermal stability of poly(3-alkylthiophene)10
remain stable and these polymers do not satisfy all the
requirements for the various possible applications. In
order to obtain a material which combines the conductivity
and chemical stability of polyanilines and the processability
of poly(3-alkylthiophenes), polyaniline derivatives have
been synthesised from commercially available substituted
anilines (methyl, ethyl, propyl).11 Nevertheless, the result-
ing polymers were insoluble in common organic solvents
and their conductivity and processability were not
significant. We therefore decided to prepare new polymers
with aniline with substituents in the ortho or meta position
or copolymers composed of aniline and substituted aniline
(Fig. 1). We developed a simple procedure for the synthesis
of such monomers allowing the introduction of a wide range
of substituents in the ortho or meta position. Large scale
(5–7 g) synthesis of monomers was required for the
polymerisation reaction in order to test their physical
properties.
We report here a general synthesis of some new ortho and
meta substituted anilines, offering a choice of substituents
and based on the low price of starting materials. The
preparation of 2-substituted alkylanilines has previously
been reported and is based on different methods such as
nitration of alkylbenzene12 and the addition of Grignard
reagents to cyanoaniline.13,14 However the latter procedure
provided a high yield only for the introduction of the propyl
group and required the use of 9 equiv. of Grignard reagents
(three examples). Wittig reactions on nitrobenzaldehyde13
were also performed but no yield was given (two examples).
Palladium catalysed cross-coupling between haloanilines
and vinyl or ethynyl metal reagents has subsequently
been proved to be efficient in the synthesis of indole
derivatives.15
An interesting procedure has recently been described invol-
ving direct alkylation of 4-haloanilines with Grignard
reagents without a protection–deprotection sequence16
under palladium salt catalysis (Scheme 1).
We therefore decided to apply this promising procedure to
the synthesis of 2- or 3-alkylanilines. Unfortunately, the
yields obtained and the purity of the coupling products
were disappointing and forced us to examine other organo-
metallic reagents.
Keywords: alkylation; anilides; coupling reactions; tin and compounds.
* Corresponding author. Tel.: ϩ33-2-47-36-69-59; fax: ϩ33-2-47-36-70-
40; e-mail: duchene@delphi.phys.univ-tours.fr
0040–4020/00/$ - see front matter ᭧ 1999 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(99)00934-5

226
A. Falcou et al. / Tetrahedron 56 (2000) 225–231
Table 1. Cross-coupling reactions of vinyltins with halogenoanilines
Entry No. Yield (%)
X
1
o-Br
Rˆn-C4H9
Rˆn-C4H9
Rˆn-C7H15
Rˆn-C7H15
Rˆn-C9H19
RˆSiMe3
2a
2b
2c
2d
2e
2f
85
71
2
3
4
5
6
7
m-Br
o-Br
m-Br
o-Br
o-Br
m-Br
67
75
61
67
71
RˆSiMe3
2g
8
o-Br
Rˆ
2h
2i
74
Figure 1. (a) Substituted aniline homopolymer; (b) copolymer composed of
aniline and substituted aniline.
9
m-Br
o-Br
Rˆ
95
10
11
RˆSnBu3
2j
2k
62
69
2,5-diBr Rˆn-C4H9
Scheme 1.
Scheme 2.
alkynes) gave the compounds 2a–2j in fair to good yields as
shown in Scheme 3.
As shown by the results reported in Table 1, the substitution
reaction appeared to have a mild and general character lead-
ing to substituted ortho- and meta-anilines. Only the (E)-
isomer (except entries 8 and 9) was reactive under our experi-
mental conditions. The scale of the products necessary for
subsequent polymerisation was reached without difficulty and
no cyclisation occurred during the process (no by-product).
The introduction of a tributylstannylvinyl unit through (E)-
bis(tributylstannyl)ethylene is reported for the first time on
bromoacetanilide (entry 10) (the synthetic potential offered
by this new compound 2j will not be studied here).19 The
introduction of two vinyl units was possible from dibromo-
acetanilide using 2.4 equiv. of vinyltin reagent (entry 11) and
providing an interesting new monomer (Scheme 4).
Scheme 3.
For the synthesis of these monomers, the retrosynthetic
scheme used is based on coupling between 2- (or 3-) halo-
anilines and vinyltins through a Stille cross-coupling
reaction (Scheme 2).
The unsaturated compounds 3a and 3c (from 2a and 2c)
were then tested for polymerisation after deprotection of
the aniline function but the unsatisfactory results obtained
led to abandoning this route. Hydrogenation of compounds
2a–2g was quantitative using the system H2/palladium
5 wt% on activated carbon,20 but was very dependent on
the presence of impurities (presence of some tin by-
products), even in very small amounts, and consequently
hydrogenation times were increased from one hour to
three days.
After some unsuccessful attempts of direct cross-coupling
between haloanilines and various vinyltins without any
protection of the amino group, we selected acetic anhydride
from the wide choice of protective methods for the amino
group offered in the literature.17 After testing all the reac-
tions on a small scale, i.e. protection, cross-coupling, hydro-
genation and deprotection, the overall yield was satisfactory
and provided clean products.
We therefore preferred to use the couple NaBH4/Ni(OAc)2
in absolute ethanol21 which provided almost the same
results but in a shorter time (3 h). The yields of the saturated
acetanilides 4a–4g are reported in Table 2. Finally the
regeneration of the aniline function with concentrated
hydrochloric acid in ethanol yielded the desired ortho-
and meta-alkylanilines 5a–5g.
After protecting the ortho- and meta-haloanilines with
acetic anhydride, the cross-coupling reaction18 in the
presence of a catalytic amount (2 mol%) of tetrakistri-
phenylphosphine palladium(0) with various vinyltins
(readily obtained by hydrostannation of the corresponding
Scheme 4.

A. Falcou et al. / Tetrahedron 56 (2000) 225–231
Table 2. Hydrogenation and deprotection of compounds 2a–2g
227
Coupling reactions with vinyltins
No.
No.
Yield (%)
No.
Yielda (%)
General procedure: 30 g (0.14 mol) of 2-bromo- or 3-
bromoacetanilide, 0.17 mol of vinyltin and 2 g (1 mol%)
of tetrakis(triphenylphosphine)palladium diluted in
250 mL of toluene are stirred overnight at 100ЊC and then
cooled to room temperature. After evaporation of the
solvent, 100 mL of a 1 M solution of potassium fluoride
and 100 mL of ethyl acetate are added to precipitate the
tributyltin bromide formed. After vigorously stirring for
2 h, the reaction mixture is filtered over Celite and extracted
with diethylether (3×100 mL). After usual work-up, the
crude products 2a–2g are purified by crystallisation (hex-
ane) or by chromatography using hexane/dichloromethane
(elution gradient).
2a
2b
2c
2d
2e
2f
(Rˆn-C4H9)
(Rˆn-C4H9)
(Rˆn-C7H15)
(Rˆn-C7H15)
(Rˆn-C9H19)
(RˆSiMe3)
(RˆSiMe3)
4a
4b
4c
4d
4e
4f
82b
98c
80b
99c
78b
85b
99c
5a
5b
5c
5d
5e
5f
90
82
71
88
75
78
76
2g
4g
5g
a Yield after deprotection and purification.
b Hydrogenation using the couple NaBH4/Ni(OAc)2 in absolute ethanol.
c Hydrogenation over H2/Pd 5 wt% on activated carbon.
In conclusion, we describe a new procedure allowing the
synthesis of ortho- and meta-alkylanilines, substituted with
a wide range of substituents, performed on a large scale
(8–10 g) with an overall yield of about 30% from the
commercially available starting haloanilines. The potential
of certain intermediates such as compounds 2j or 2k were
not exploited in this work.
2-[Hex-10-enyl]acetanilide 2a. IR (cmϪ1): 3289, 3040,
1654, 1532.
3
1H NMR (200 MHz): 0.97 (3H, t, J2Hˆ6.9 Hz), 1.30–1.60
(4H, m), 2.15–2.40 (2H, m), 2.24 (3H, s), 6.14 (1H, dt,
3
3
3J1Hˆ15.8 Hz, J2Hˆ7.0 Hz), 6.45 (1H, d, J1Hˆ15.8 Hz),
3J1Hˆ7.8 Hz).
3
7.10–7.27 (2H, m), 7.38 (1H, d, J1Hˆ7.1 Hz), 7.88 (1H, d,
Some of them (5a–5g) are currently being tested for poly-
merisation or copolymerisation and are providing promising
results in terms of solubility, conductivity and process-
ability. The polymerisation process and characterisation of
these polymers are currently underway and will be reported
in due course.22
13C NMR (50 MHz): 14.5, 22.8, 24.8, 32.0, 33.6, 123.9,
125.2, 125.7, 127.7, 128.2, 131.3, 134.7, 136.4, 168.8.
⅐
MS: m/zˆ217 (M , 18), 175 (14), 174 (100), 146 (13), 132
(70), 131 (11), 130 (27), 119 (13), 118 (74), 117 (35), 115
(17), 106 (31), 91 (13), 77 (18), 43 (59), 41 (14), 39 (10).
3-[Hex-10-enyl]acetanilide 2b. IR (cmϪ1): 3295, 1668,
Experimental
1557.
All reactions were carried out under inert atmosphere (Ar or
N2). THF, ether and toluene were freshly distilled over
sodium/benzophenone ketyl and CH2Cl2 over calcium
hydride. Flash chromatographies were performed on silica
gel 230–400 mesh. GLC analyses were performed on a
Perkin–Elmer instrument (FID detector, fitted with a
1H NMR (200 MHz): 0.96 (3H, t, J2Hˆ6.7 Hz), 1.34–1.60
3
(4H, m), 2.15–2.30 (2H, m), 2.21 (3H, s), 6.17–6.42 (2H,
3
m), 7.12 (1H, d, J1Hˆ7.3 Hz), 7.21–7.38 (2H, m), 7.54
(1H, s).
1
25 m×0.32 mm SE 52 capillary column). H NMR spectra
13C NMR (50 MHz): 14.5, 22.8, 24.9, 32.0, 33.2, 118.3,
119.2, 122.5, 129.5, 129.9, 132.3, 138.9, 139.4, 169.7.
were recorded on a Bruker AC 200. Data, reported using
the residual solvent proton resonance of CDCl3
(dHˆ7.25 ppm) as the internal reference, are as follows in
the order: chemical shift (d in ppm relative to Me4Si), multi-
plicity (s, d, t, q, m, b for singlet, doublet, triplet, quartet,
multiplet and broad, respectively), coupling constants
(J in Hz). 13C NMR were recorded at 50 MHz on the
same instrument, using the CDCl3 solvent peak at
dCˆ77.0 ppm as the reference. Mass spectra were obtained
on a Hewlett Packard apparatus (engine 5989A) in GC/MS
mode (70 eV). IR spectra were recorded on a Nicolet
250 FT-IR spectrophotometer.
⅐
MS: m/zˆ217 (M , 52), 188 (14), 175 (28), 174 (23), 161
(17), 149 (15), 146 (41), 133 (27), 132 (100), 120 (12), 119
(40), 118 (10), 117 (28), 115 (27), 107 (29), 106 (17), 103
(12), 93 (10), 91 (17), 77 (19), 65 (12), 43 (74), 41 (16), 39
(13).
2-[Non-10-enyl]acetanilide 2c. IR (cmϪ1): 3289, 3035,
1656, 1532.
1H NMR (200 MHz): 0.93 (3H, t, J2Hˆ6.6 Hz), 1.22–1.62
3
(10H, m), 2.15–2.40 (2H, m), 2.24 (3H, s), 6.15 (1H, dt,
3
3
(E)-1-Trimethylsilyl-2-n-tributylstannylethylene was pre-
pared according to Ref. 23, (E)-1,2-bis(tributylstannyl)-
ethylene was prepared according to Ref. 24, other vinyltin
reagents were prepared by hydrostannation of the corre-
sponding terminal alkynes under radicalar conditions
(AIBN) and used as a thermodynamic mixture of (E) and
(Z)-isomers.25 All new compounds gave satisfactory micro-
analysis (C, H^0.5) performed by the ‘Service Central
d’Analyse’ of the CNRS in Vernaison.
3J1Hˆ15.7 Hz, J2Hˆ6.8 Hz), 6.45 (1H, d, J1H ˆ 15.7 Hz),
3
7.10–7.27 (2H, m), 7.39 (1H, d, J1Hˆ6.8 Hz), 7.87 (1H, d,
3J1Hˆ7.8 Hz).
13C NMR (50 MHz): 14.7, 23.2, 24.7, 29.7, 29.8, 29.9, 32.4,
33.9, 124.4, 125.2, 125.8, 127.5, 128.1, 130.6, 134.7, 135.9,
169.1.
⅐
MS: m/zˆ259 (M , 15), 217 (18), 216 (100), 146 (18), 144

228
A. Falcou et al. / Tetrahedron 56 (2000) 225–231
(13), 133 (10), 132 (78), 131 (15), 130 (36), 119 (17), 118
(80), 117 (39), 115 (18), 107 (12), 106 (51), 91 (11), 77 (13),
57 (29), 43 (76), 41 (23).
1H NMR (200 MHz): 0.16 (9H, s), 2.18 (3H, s), 6.49 (1H, d,
3
3J1Hˆ19.1 Hz), 6.85 (1H, d, J1Hˆ19.1 Hz), 7.16–7.30
3
(2H, m), 7.40 (1H, d, J1Hˆ8.1 Hz), 7.74 (1H, m), 8.53
(1H, bs).
Anal. Calcd for C17H27NO: C, 78.09; H, 10.42; N, 5.36.
Found: C, 78.21; H, 10.39; N, 5.37.
13-C NMR (50 MHz): Ϫ1.38, 24.8, 117.9, 119.5, 122.3,
128.9, 130.1, 138.2, 139.1, 143.0, 169.
3-[Non-10-enyl]acetanilide 2d. IR (cmϪ1): 3302, 1666,
1556.
⅐
MS: m/zˆ233 (M , 29), 218 (45), 203 (17), 202 (100), 176
(14), 161 (12), 160 (17), 116 (37), 73 (15), 59 (27), 45 (12),
43 (36).
3
1H NMR (200 MHz): 0.93 (3H, t, J2Hˆ7.2 Hz), 1.20–1.70
(10H, m), 2.15–2.30 (2H, m), 2.21 (3H, s), 6.10–6.42 (2H,
3
m), 7.12 (1H, d, J1Hˆ7.4 Hz), 7.23–7.34 (2H, m), 7.54
2-[40,40-Diethoxybut-10-enyl]acetanilide 2h. IR (cmϪ1):
3401, 1660, 1546.
(1H, s).
1
3
13C NMR (50 MHz): 14.6, 23.2, 25.1, 29.7, 29.9, 32.4, 33.6,
117.9, 118.9, 122.5, 129.6, 129.9, 132.5, 138.7, 139.5, 168.9.
Z isomer: H NMR (200 MHz): 1.21 (6H, t, J2Hˆ7.0 Hz),
3
3
2.18 (3H, s), 2.42 (2H, dd, J1Hˆ7.2 Hz, J1Hˆ5.4 Hz),
3
3.41–3.70 (4H, m), 4.56 (1H, t, J2Hˆ5.4 Hz), 5.98 (1H,
⅐
3
3
3
MS: m/zˆ259 (M , 67), 217 (15), 202 (10), 188 (19), 175
dt, J1Hˆ11.1 Hz, J2Hˆ7.2 Hz), 6.48 (1H, d, J1Hˆ
11.1 Hz), 7.09–7.29 (3H, m), 7.42 (1H, bs), 8.14 (1H, d,
3J1Hˆ7.7 Hz).
(11), 174 (40), 162 (20), 161 (53), 149 (63), 146 (34), 144
(12), 133 (28), 132 (100), 120 (15), 119 (62), 118 (10), 117
(26), 115 (24), 107 (50), 106 (22), 91 (13), 77 (12), 43 (74),
41 (26), 39 (10).
1
3
E isomer: H NMR (200 MHz): 1.26 (6H, t, J2Hˆ7.7 Hz),
3
3
2.21 (3H, s), 2.59 (2H, dd, J1Hˆ7.2 Hz, J1Hˆ5.3 Hz),
2-[Undec-10-enyl]acetanilide 2e. IR (film, cmϪ1): 3287,
3034, 1656, 1532.
3.49–3.79 (4H, m), 4.62 (1H, t, J2Hˆ5.3 Hz), 6.10 (1H,
3
3
3
3
dt, J1Hˆ15.6 Hz, J2Hˆ7.2 Hz), 6.54 (1H, d, J1Hˆ
15.6 Hz), 7.09–7.39 (3H, m), 7.53 (1H, bs), 7.84 (1H, d,
3J1Hˆ7.7 Hz).
3
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.4 Hz), 1.20–1.64
(14H, m), 2.15–2.40 (2H, m), 2.23 (3H, m), 6.14 (1H, dt,
3J1Hˆ15.7 Hz, J2Hˆ6.8 Hz), 6.45 (1H, d, J1Hˆ15.7 Hz),
3J1Hˆ8.0 Hz).
13C NMR (50 MHz): 15.2, 24.1, 37.8, 61.4, 102.1, 123.5,
125.0, 126.9, 127.4, 127.7, 129.4, 130.7, 132.4, 168.6.
3
3
3
7.10–7.30 (2H, m), 7.39 (1H, d, J1Hˆ6.8 Hz), 7.89 (1H, d,
⅐
MS: m/zˆ277 (M , 1), 144 (12), 132 (21), 118 (13), 117
13C NMR (50 MHz): 14.7, 23.2, 24.6, 29.8, 29.9, 30.1, 30.2,
32.4, 33.9, 124.0, 125.1, 125.7, 127.7, 128.2, 130.9, 134.7,
136.4, 169.1.
(19), 115 (11), 103 (94), 77 (11), 75 (82), 47 (100), 43 (60).
Anal. Calcd for C16H23NO3: C, 69.27; H, 8.36; N, 5.05.
Found: C, 69.32; H, 8.32; N, 5.02.
⅐
MS: m/zˆ287 (M , 13), 245 (19), 244 (100), 148 (10), 146
(117), 144 (13), 133 (10), 132 (66), 131 (11), 130 (29), 119
(15), 118 (78), 117 (31), 115 (13), 107 (15), 106 (61), 77
(10), 57 (18), 55 (10), 43 (98), 41 (30).
3-[40,40-Diethoxybut-10-enyl]acetanilide 2i. IR (film,
cmϪ1): 3309, 1669, 1553.
1
3
Z isomer: H NMR (200 MHz): 1.18 (6H, t, J2Hˆ8.8 Hz),
3
3
Anal. Calcd for C19H31NO: C, 78.83; H, 10.80; N, 4.84.
Found: C, 78.91; H, 10.76; N, 4.86.
2.13 (3H, s), 2.68 (2H, dd, J1Hˆ7.1 Hz, J1Hˆ5.7 Hz),
3
3.53–3.77 (4H, m), 4.60 (1H, t, J2Hˆ5.7 Hz), 5.72 (1H,
3
3
3
dt, J1Hˆ11.8 Hz, J2Hˆ7.1 Hz), 6.48 (1H, d, J1Hˆ
2-[20-Trimethylsilylethenyl]acetanilide 2f. IR (cmϪ1):
11.8 Hz), 7.03–7.44 (4H, m).
3225, 1660, 1538,1481, 838.
1
3
E isomer: H NMR (200 MHz): 1.26 (6H, t, J2Hˆ8.8 Hz),
1H NMR (200 MHz): 0.21 (9H, s), 2.25 (3H, s), 6.45 (1H, d,
2.20 (3H, s), 2.57 (2H, dd, J1Hˆ6.9 Hz, J1Hˆ5.7 Hz),
3
3
3J1Hˆ19.0 Hz), 6.97 (1H, d, J1Hˆ19 Hz), 7.10–7.37 (2H,
3.53–3.77 (4H, m), 4.58 (1H, t, J2Hˆ5.7 Hz), 6.23 (1H,
3
3
3
3
3
3
3
m), 7.49 (1H, d, J1Hˆ7.1 Hz), 7.83 (1H, d, J1Hˆ8.1 Hz).
dt, J1Hˆ15.8 Hz, J2Hˆ6.9 Hz), 6.46 (1H, d, J1Hˆ
15.8 Hz), 7.11–7.53 (4H, m).
13C NMR (50 MHz): Ϫ0.71, 24.8, 124.9, 126.1, 127.2,
128.9, 132.4, 134.7, 134.9, 139.2, 169.2.
13C NMR (50 MHz): 15.2, 24.3, 37.7, 61.4, 102.4, 117.6,
118.7, 121.8, 125.6, 128.8, 131.9, 138.1, 138.2, 168.9.
⅐
MS: m/zˆ233 (M , 5), 190 (41), 160 (13), 144 (65), 118
⅐
(11), 75 (11), 73 (100), 45 (12), 43 (30).
MS: m/zˆ277 (M , 1), 144 (19), 143 (13), 132 (26), 130
(13), 117 (11), 103 (100), 75 (80), 47 (92), 43 (52).
Anal. Calcd for C13H19NOSi: C, 66.92; H, 8.21; N, 6.00.
Found: C, 67.01; H, 8.19; N, 6.03.
2-[20-Tributylstannylethenyl]acetanilide 2j. IR (cmϪ1):
3274, 3042, 1652, 1531.
3-[20-Trimethylsilylethenyl]acetanilide 2g. IR (cmϪ1):
3222, 1665, 1538,1483, 828.
1H NMR (200 MHz): 0.80–1.20 (15H, m), 1.22–1.80 (12H,

A. Falcou et al. / Tetrahedron 56 (2000) 225–231
229
3
m), 2.19 (1H, s), 6.79 (1H, d, 3J1Hˆ19.4 Hz,
1H NMR (200 MHz): 0.91 (3H, t, J2Hˆ6.3 Hz), 1.32 (6H,
3
2
3
3JSn-Hˆ66.6 Hz), 6.99 (1H, d, J1Hˆ19.4 Hz, JSn-H
ˆ
m), 1.63 (2H, m), 2.19 (3H, s), 2.61 (2H, t, J2Hˆ7.6 Hz),
3
3
61.2 Hz), 7.21 (2H, m), 7.43 (1H, d, J1Hˆ6.0 Hz), 7.80
6.96 (1H, d, J1Hˆ7.3 Hz), 7.21–7.44 (3H, m).
3
(1H, d, J1H ˆ 7.7 Hz).
13C NMR (50 MHz): 14.6, 23.1, 24.9, 29.5, 31.9, 32.3, 36.5,
117.9, 120.6, 124.9, 129.3, 138.6, 144.5, 169.3.
13C NMR (50 MHz): 9.59 (1JSn-Cˆ345–330 Hz), 13.6, 24.2,
27.2 (3JSn-Cˆ42–54 Hz), 29.0 (2JSn-Cˆ20.5 Hz), 125.0,
126.0, 127.1, 128.4, 133.4, 134.5, 134.8, 142.2, 169.2.
⅐
MS: m/zˆ219 (M , 20), 177 (19), 149 (24), 120 (12), 107
(100), 106 (28), 79 (10), 77 (11), 43 (37), 41 (11).
⅐
MS: m/zˆ394 (M Ϫ57, 95), 338 (13), 282 (9), 254 (18), 252
(15), 177 (12), 144 (100), 118 (39), 43 (45).
2-Nonylacetanilide 4c. IR (film, cmϪ1): 3275, 3039, 1654,
1536.
2-5-Di[hex-10-en-1-yl]acetanilide 2k. IR (cmϪ1): 3263,
3021, 1664.
3
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.5 Hz), 1.30
1H NMR (200 MHz): 0.95 (6H, t, J2Hˆ6.9 Hz), 1.42 (8H,
3
(12H, m), 1.61 (2H, m), 2.21 (3H, s), 2.60 (2H, t,
3J2Hˆ7.5 Hz), 7.10–7.30 (3H, m), 7.71 (1H, d, J1Hˆ
3
m), 2.15–2.30 (4H, m), 2.24 (3H, m), 6.08 (1H, dt,
3J1Hˆ15.9 Hz, J2Hˆ7.0 Hz), 6.20–6.44 (3H, m), 7.11
3
7.4 Hz).
(1H, d,3J1Hˆ8.7 Hz), 7.35 (1H, d, J1Hˆ8.7 Hz), 7.77
3
13C NMR (50 MHz): 14.6, 23.2, 24.9, 29.8, 30.1 (3C), 30.4,
31.9, 32.4, 127.3 (3C), 130.0, 134.6, 135.7, 168.4.
(1H, s).
13C NMR (50 MHz): 14.5, 22.8, 24.5, 32.0, 33.3, 33.6,
122.5, 125.2, 129.8, 123.6, 127.1, 130.2, 134.7, 131.8,
134.6, 137.9, 168.8.
⅐
MS: m/zˆ261 (M , 7), 218 (15), 162 (10), 149 (10), 120
(12), 107 (23), 106 (100), 43 (41), 41 (18).
2-Undecylacetanilide 4e. IR (cmϪ1): 3270, 3040, 1652,
1537.
⅐
MS: m/zˆ299 (M , 23), 256 (100), 230 (11), 214 (16), 200
(14), 186 (47), 174 (31), 170 (12), 168 (12), 158 (13), 156
(25), 145 (10), 144 (61), 143 (20), 132 (20), 131 (14), 130
(38), 129 (14), 128 (14), 117 (10), 115 (15), 55 (41), 43 (80),
41 (38), 39 (10).
3
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.4 Hz), 1.30 (16H,
3
m), 1.61 (2H, m), 2.23 (3H, s), 2.60 (2H, t, J2Hˆ7.6 Hz),
3
7.10–7.30 (2H, m), 7.51 (1H, d, J1Hˆ7.6 Hz), 7.63 (1H, d,
3J1Hˆ7.4 Hz).
Anal. Calcd for C20H29NO: C, 80.21; H, 9.77; N, 4.68.
Found: C, 80.33; H, 9.73; N, 5.67.
13C NMR (50 MHz): 14.0, 22.6, 24.2, 29.2, 29.4 (3C), 29.5
(2C), 29.7, 31.2, 31.8, 124.1, 125.4, 126.5, 129.3, 133.9,
134.8, 168.4.
Hydrogenation of the double bond20,21
⅐
MS: m/zˆ289 (M , 10), 246 (18), 162 (11), 149 (10), 120
General procedure: To 0.10 mol of compound 2 dissolved
in 250 mL of absolute ethanol were added 5 g (20 mmol) of
nickel(II) acetate tetrahydrate then the solution was gently
warmed until the solution was homogenous. The mixture
was cooled to 0ЊC and 1.9 g (0.05 mol) of sodium borohy-
dride dissolved in 50 mL of ethanol were added dropwise
with stirring. After completion of the reaction, the solution
was hydrolysed with 100 mL of a saturated solution of am-
monium chloride, filtered over Celite and extracted with
dichloromethane (3×300 mL). After usual work-up, the
crude products were clean enough and could be used with-
out further purification.
(12), 107 (23), 106 (100), 43 (53), 41 (26).
2-[20-Trimethylsilylethyl]acetanilide 4f. IR (cmϪ1): 3258,
1653, 1533, 1462, 832.
1H NMR (200 MHz): 0.08 (9H, s), 0.82 (2H, m), 2.21 (3H,
s), 2.58 (2H, m), 7.09–7.30 (3H, m), 7.68 (1H, d,
3J1Hˆ6.4 Hz).
13C NMR (50 MHz): Ϫ1.2, 17.9, 24.8, 26.3, 125.0, 126.3,
127.1, 129.4, 135.3, 137.4, 169.0.
⅐
2-Hexylacetanilide 4a. IR (cmϪ1): 3278, 3039, 1654, 1534.
MS: m/zˆ235 (M , 9), 220 (26), 192 (17), 178 (27), 162
(17), 146 (14), 144 (11), 120 (19), 106 (14), 75 (13), 74
(10), 73 (100), 59 (11), 45 (25), 43 (53).
3
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.3 Hz), 1.35 (6H,
3
m), 1.60 (2H, m), 2.20 (3H, s), 2.58 (2H, t, J2Hˆ7.6 Hz),
3-[20-Trimethylsilylethyl]acetanilide 4g. IR (cmϪ1): 3321,
1667, 1557, 1483, 830.
3
7.19–7.41 (3H, m), 7.67 (1H, d, J1Hˆ7.4 Hz)
13C NMR (50 MHz): 14.7, 23.2, 23.9, 29.7, 30.4, 31.8, 32.2,
126.5, 126.6, 129.8, 135.8, 137.2, 170.4.
1H NMR (200 MHz): 0.05 (9H, s), 0.89 (2H, m), 2.20 (3H,
3
s), 2.64 (2H, m), 6.99 (1H, d, J1Hˆ6.97 Hz), 7.21–7.33
⅐
(3H, m), 7.43 (1H, s large).
MS: m/zˆ219 (M , 9), 176 (14), 120 (12), 107 (21), 106
(100), 77 (11), 43 (30).
13C NMR (50 MHz): Ϫ1.85, 18.4, 24.4, 29.9, 117.3, 119.3,
123.7, 128.9, 137.8, 146.2, 168.6.
3-Hexylacetanilide 4b. IR (cmϪ1): 3290, 1665, 1557.

230
A. Falcou et al. / Tetrahedron 56 (2000) 225–231
⅐
⅐
MS: m/zˆ235 (M , 45), 234 (26), 220 (28), 205 (12), 204
(71), 192 (14), 144 (12), 116 (26), 75 (11), 74 (12), 73 (100),
59 (24), 45 (25), 43 (37).
MS: m/zˆ219 (M , 12), 120 (13), 107 (100), 106 (31),
41(10).
2-Undecylaniline 5e. IR (cmϪ1): 3471, 3379, 1621, 1498,
1458.
Regeneration of the amino group26
1H NMR (200 MHz): 0.95 (3H, t, J2Hˆ6.3 Hz), 1.25–1.39
3
General procedure: 0.10 mol of acetanilide 4 in 50 mL of
ethanol and 150 mL of concentrated hydrochloric acid were
refluxed for 10 h. After cooling, the mixture was treated
with a 5% solution of sodium hydroxide, extracted with
diethylether (2×200 mL) and dried over MgSO4. The
obtained alkylaniline 5 was then purified by column
chromatography (petroleum ether/diethylether: 80/20).
(16H, m), 1.68 (2H, m), 2.54 (2H, t, 3J2Hˆ7.7 Hz), 3.67 (2H,
bs), 6.56–6.83 (2H, m), 7.09 (2H, m).
13C NMR (50 MHz): 14.2, 22.7, 28.8, 29.5, 29.6, 29.7, 29.8
(2C), 29.9, 31.3, 32.0, 115.5, 118.7, 126.8, 126.9, 129.4,
144.0.
⅐
MS: m/zˆ247 (M , 20), 107 (16), 106 (100), 41 (13).
2-Hexylaniline 5a. IR (cmϪ1): 3467, 3378, 1621, 1498,
1457.
Anal. Calcd for C17H29N: C, 82.51; H, 11.82; N, 5.66.
Found: C, 82.50; H, 11.84; N, 5.65.
1H NMR (200 MHz): 0.96 (3H, t, J2Hˆ6.4 Hz), 1.39 (6H,
3
3
m), 1.67 (2H, m), 2.54 (2H, t, J2Hˆ7.7 Hz), 3.65 (2H, bs),
2-[20-Trimethylsilylethyl]aniline 5f. IR (film, cmϪ1):
3466, 3376, 1621, 1496, 1248, 835.
6.71–6.83 (2H, m), 7.08 (2H, m).
13C NMR (50 MHz): 14.9, 23.5, 29.5, 30.2, 31.2, 32.6,
116.3, 119.4, 127.6, 130.1, 145.0.
1H NMR (200 MHz): 0.09 (9H, s), 0.91 (2H, m), 2.53 (2H,
m), 3.70 (2H, bs), 6.71–6.83 (2H, m), 7.04–7.16 (2H, m).
⅐
MS: m/zˆ177 (M , 16), 107 (15), 106 (100), 77 (15), 41
13C NMR (50 MHz): Ϫ1.1, 16.2, 25.9, 116.1, 119.5, 127.3,
129.8 (2C), 144.4.
(10).
⅐
3-Hexylaniline 5b. IR (cmϪ1): 3434, 3351, 1621, 1462.
MS: m/zˆ193 (M , 42), 179 (14), 178 (89), 161 (32), 150
(28), 134 (13), 120 (21), 119 (13), 106 (99), 91 (10), 77(19),
74 (16), 73 (100), 59 (34), 45 (33), 44 (11), 43 (12).
3
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.4 Hz), 1.35 (6H,
3
m), 1.59 (2H, m), 2.55 (2H, t, J2Hˆ7.7 Hz), 3.3 (2H, bs),
6.54–5.65 (3H, m), 7.11 (1H, m).
3-[20-Trimethylsilylethyl]aniline 5g. IR (cmϪ1): 3471,
3371, 1614, 1248.
13C NMR (50 MHz): 14.7, 23.3, 29.7, 32.0, 32.4, 36.7,
113.2, 115.9, 119.5, 129.7, 144.8, 147.0.
1H NMR (200 MHz): 0.09 (9H, s), 0.91 (2H, m), 2.60 (2H,
m), 3.49 (2H, bs), 6.55–6.71 (3H, m), 7.17 (1H, t,
3J1Hˆ7.64 Hz).
13C NMR (50 MHz): Ϫ1.81, 18.4, 29.9, 112.5, 114.6, 118.1,
129.2, 146.2, 146.5.
⅐
MS: m/zˆ177 (M , 10), 120 (11), 107 (100), 106 (40), 79
(10), 77 (13).
2-Nonylaniline 5c. IR (cmϪ1): 3468, 3378, 1621, 1498,
1457.
⅐
MS: m/zˆ193 (M , 60), 179 (10), 178 (60), 150 (50), 120
1H NMR (200 MHz): 0.92 (3H, t, J2Hˆ6.3 Hz), 1.20–1.47
(13), 119 (15), 74 (22), 73 (100), 59 (42), 45 (22), 43 (10).
3
(12H, m), 1.66 (2H, m), 2.52 (2H, t, 3J2Hˆ7.7 Hz), 3.67 (2H,
bs), 6.70–6.81 (2H, m), 7.07 (2H, m).
Anal. Calcd for C11H19NSi: C, 68.35; H, 9.91; N, 7.25.
Found: C, 68.29; H, 9.89; N, 7.25.
13C NMR (50 MHz): 14.7, 23.2, 29.4, 29.9, 30.1 (2C), 30.3,
31.9, 32.5, 116.2, 119.4, 127.4, 127.7, 130.0, 144.4.
2-[Hex-10-enyl]aniline 3a. IR (cmϪ1): 3456, 3374, 1618,
1456.
⅐
MS: m/zˆ219 (M , 10), 107 (17), 106 (100).
1H NMR (200 MHz): 0.97 (3H, t, J2Hˆ7.0 Hz), 1.47 (4H,
3
Anal. Calcd for C15H25N: C, 82.12; H, 11.49; N, 6.39.
Found: C, 82.22; H, 11.48; N, 6.38.
m), 2.27 (2H, dt, 3J2Hˆ6.7 Hz, 3J1Hˆ6.7 Hz), 3.68 (2H, bs),
3
3
6.12 (1H, dt, J1Hˆ15.6 Hz, J2Hˆ6.8 Hz), 6.45 (1H, d,
3J1Hˆ15.6 Hz), 6.70–6.83 (2H, m), 7.09 (1H, dt,
4
3
3-Nonylaniline 5d. IR (cmϪ1): 3457, 3371, 1619, 1462.
3J1Hˆ7.7 Hz, J1Hˆ1.5 Hz), 7.27 (1H, dd, J1Hˆ7.7 Hz,
4J1Hˆ1.5 Hz).
3
1H NMR (200 MHz): 0.93 (3H, t, J2Hˆ6.4 Hz), 1.32 (12H,
3
m), 1.63 (2H, m), 2.56 (2H, t, J2Hˆ7.7 Hz), 3.3 (2H, bs),
13C NMR (50 MHz): 14.7, 23.0, 32.4, 33.8, 116.7, 119.6,
125.1, 126.1, 128.0, 128.5, 133.8, 144.1.
6.54–6.65 (3H, m), 7.11 (1H, m).
⅐
13C NMR (50 MHz): 14.7, 23.3, 29.9, 30.0, 32.2 (2C), 31.9,
32.5, 36.6, 113.1, 115.9, 119.5, 129.7, 144.8, 146.9.
MS: m/zˆ217 (M , 35), 133 (12), 132 (100), 119 (15), 118
(65), 117 (26), 115 (14), 107 (13), 106 (90), 93 (12), 41 (10).

A. Falcou et al. / Tetrahedron 56 (2000) 225–231
231
2-[Nona-10-enyl]aniline 3c. IR (cmϪ1): 3456, 3377, 1618,
1456.
Miyadera, H.; Kosehi, M.; Kobayashi, Y. Synth. Met. 1989, 28,
`
C639. (d) Genies, E. M.; Boyle, A.; Lapkowski, M.; Tsintavis, C.
Synth. Met. 1990, 36, 139.
3
1H NMR (200 MHz): 1.20 (3H, t, J2Hˆ6.7 Hz), 1.59 (10H,
8. Ballauff, M. Angew. Chem., Int. Ed. Engl. 1989, 28, 253.
9. (a) Elsenbaumer, R. L.; Jen, K. Y.; Oboodi, R. Synth. Met. 1986,
15, 169. (b) Sato, M. A.; Tanaka, S.; Kaerigana, K. J. Chem. Soc.
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m), 2.48 (2H, dt, 3J2Hˆ6.7 Hz, 3J1Hˆ6.7 Hz), 3.90 (2H, bs),
3
3
6.34 (1H, dt, J1Hˆ15.7 Hz, J2Hˆ6.8 Hz), 6.64 (1H, d,
3
3J1Hˆ15.7 Hz), 6.81 (1H, d, J1Hˆ7.9 Hz), 6.99 (1H, dt,
3
4
3J1Hˆ7.4 Hz), 7.27 (1H, dd, J1Hˆ7.5 Hz, J1Hˆ1.5 Hz),
3
¨
7.49 (1H, d, J1Hˆ7.6 Hz).
10. Granstrom, M.; Inganas, O. Synth. Met. 1992, 48, 21.
`
11. (a) Bidan, G.; Genies, E. M.; Penneau, J. F. J. Electroanal.
13C NMR (50 MHz): 14.3, 22.9, 29.4 (2C), 29.7, 32.0, 33.6,
116.1, 118.9, 124.5, 125.6, 127.4, 127.9, 133.0, 143.4.
Chem. 1989, 271, 59–68. (b) Wei, Y.; Focke, W. W.; Wnek, G. E.;
Ray, A.; MacDiarmid, A. G. J. Phys. Chem. 1989, 93, 495–499. (c)
Gupta, M. C.; Umare, S. S. Macromolecules 1992, 25, 138–142.
(d) Pouget, J. P.; Zhao, S. L.; Wang, Z. H.; Oblakowski, Z.;
Epstein, A. J.; Manohar, S. K.; Wiesinger, J. M.; MacDiarmid,
A. G.; Hsu, C. H. Synth. Met. 1993, 55–57, 341–346. (e)
Ahmad, N.; Feng, P.; Schursky, H.; Shah, S.; Antonacci, D.;
Cichowicz, M. B. Indian J. Chem. 1993, 32A, 673–678.
⅐
MS: m/zˆ217 (M , 35), 133 (12), 132 (100), 119 (15), 118
(65), 117 (26), 115 (14), 107 (13), 106 (90), 93 (12), 41 (10).
Acknowledgements
`
¨
12. Genies, E. M.; Noel, P. J. Electroanal. Chem. 1991, 310,
89–111.
We thank the CNRS and MESR for providing financial
support and a fellowship to one of us (A.F.), and the
13. Bodalia, R.; Stern, R.; Batich, C.; Duran, R. J. Polym. Sci. Part
A: Polym. Chem. 1993, 31 (8), 2123–2127.
14. Sikkar, R.; Martinson, P. Acta Chem. Scand. 1990, B34,
551–557.
´
‘Service des caracterisations physico-chimiques du CEA
Le Ripault’ for recording NMR and mass spectra.
15. (a) Sakamoto, S.; Kondo, Y.; Yasuhara, A.; Yamanaka, H.
Tetrahedron 1991, 47, 1877–1886. (b) Krolski, M. E.; Renaldo,
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